Taljafebro james faffiley



Patented Nov. 10, 1931 UNITED sr 'ras PATENT om-" ce J TALIAI'ERBO JAMES FAIBLEY, OI STERLING-TON, LOUISIANA, ASSIGNOR, BY DIRECT AND HESNE ASSIGNMENTS, OF ONE-HALF '1'0 W. J. HUNTER AND ONE-HALF TO MARY P. HUNTER, BOTH OF SHREVEPOR'I', LOUISIANA exams or TREATING OILS No Drawing. Application filed May 21,

The present invention relates to the treatment by distillation of a variety of oils which may be particularly described as oils of the animal and vegetable series, essential oils, the members of all of which series are well known, and to a series of hydrocarbons known as the terpenes, the latter class being generally recognized as containing a compound having the empirical formula 0 B 10 In this latter series are contained various wood oils, pine oils, oils which are the prodnet of wood distillation, oils obtained from various pine oils, resin oils, tar oils, oils from resinous wood, sawdust, and also oils which are roduced by the treatment of tree and vegeta le gums. Y

I The object of the invention is to distill any one of the oils of the several series men- 'tioned in such a manner as to obtain a diszo tillate and a residual roduct, both of which are found to have.mar l (ed advantages, due to their physical and chemical constitution.

For example, the distillate obtained has been found to have a marked importance as a'solvent particularly in connection with the reclaiming of vulcanized rubber.

The oil residue which remains, and which may be further treated by various refining methods, if necessary, has been found to possess characteristics definitely indicating its usefulness as alubricating oil equal to the best ades of the mineral product.

One of ixhe most important features of the process resides in the use of an agent, for example a clay and particularly a colloidal clay having all or some of the properties of bentonite, which apparently does not enter into the reaction, but the presence of which changes the physical and chemical constitu- 40 tion of the material being distilled, so that the distillate recovered as well as the residual oil, has marked characteristics which dis tinguish it from the original charge.

While my invention,'as stated, is applicable to animal and vegetable oils,essential oils and various other oils, I have found it particularly useful and advantageous in connection with oils of the terpene' series and their homologues. There is, of course, a large number of 1928. sum no. 279,005.

with turpentine, probably the most representative andimportant of the terpenes, and it will be understood that the turpentine may be that produced in wood distillation as well as the usual and well known gum spirits of turpentine. -It will be understood that in mentioning these two, they are simply for, purposes of illustration and I do not confine myself by any means to these specific terpenes. 1 i

In carrying out the invention the turpentine from either of the above sources is run into a suitable still in which there has been charged a sufficient quantity of, clay which is arranged in a position where it may suitably come in contact with the turpentine. The quantity of clay, of course, will depend upon the bulkof turpentine to be treated and may be described for some cases as ten per cent by weight of the turpentine. This is only approximate and may be varied at will, .depending upon the nature of the 0 product, the apparatus and the end products which it is desired to obtain.

With the turpentine and-clay in the still, the mass is gently or slowly heated for a short period or until it has the appearance of boil- 85, in a After the mass has reached a temperature which produces a slow boiling, the temperature is maintained for a short period to continue the mass in this condition.

During this preliminary or initial heating a small amount of distillate will, of course, pass off as vapor which will be condensed and collectedand the small amount of water separated. In some casesfit is advantageous tomaintain the vapors produced by these K steps in the still pending further operation of the process. 1

It will be understood that in some cases this preliminary treatment or treatments will not Of course, during the heating period, the

clay coming in contact with the material will cause chemical reaction and rearran ment and physical changes resulting in the ormation of new compoun s and also this reformation will continue to some extent during the subsequent distillation. The amount and s eed with which the chemical and physical c anges take place will, of course, vary with the conditions surrounding the heating and distilling operation, so that in some cases rapid reaction will take place, while in other cases, the reaction will be slow and may not occur completely until the subsequent fractionation is in progress.

It is enough to say, however, that b reason of the process which I employ, the c aracter of theoil under treatment, in this particular case turpentine, undergoes a physical and chemical change, resulting in t e fractional cuts obtained. This may be due in some cases to a cracking efl'ect upon the oil induced by the distillation in the presence of the clay.

When a suflicient time has elapsed and it would appear that the contact between the oil and clay has been adequate, the temperature of the still is raised gradually to distil or fractionate the various volatile constituents of the oil.

This fractionating generally continues to a point-in the neighborhood of 250 0., where have found with usual runs of turpentine that the lighter fractions cease to come over and a heavuer fraction begins to come ofi. I may stop at this point unless it is desired to have a distillate containing a portion or all .of the heavier fractions. Where I have continued distillation. beyond 250 0. the distillate shows a greenish tint and fluorescence and has the characteristics of a light lubricant indicatingthe presence of oily fractions.

' Such distillate may in some cases be used as a lubricant, rust remover, a gun oil and for 7 other purposes, as furniture polish and floor oils. The oil content will, of course, increase in the distillate as the fractionating temperature rises above substantially 250 0. I have found that a distillate containing a greater or less quantity of the heavy fractions may be used as a lubricant for purposes dependent upon the weight of oil r uired.

In the fractionating o the turpentine in the presence of .the clay, I observe that the fractions at various stages specific gravities, for example some 0 the fractions at the increased temperature range have a lighter specific avity than those of a lower boiling range. orexample, the distillate collected up to 180 0. has a specific.

gravit of 0353-0855, that from 180 to 190 a ific gravity of 0.844 and that from 190 to 250 0. a specific'gravity of 0.862. The figures 'ven are at 15.5 C. and of course result wit the use of clay as described.

cases the fractions which are taken ofi up to substantially 250 0. are of relatively lig ter specific gravity than the material treated,

tar,

It suflices, however, to say that in most while above thispoint the fractions usually have a viscous character.

I stop primarily at the point where the heavy viscous fractions'wouldbegin to come over because the distillate produced up to.

this point is valuable as a solvent and this qualit is sometimes changed after an apprecia- 1e rtion of the heavier fractions are mixed wit such distillate. Such a distillate having an oily content to various degrees, however, may -be used as a lubricant if desired. I 1

Moreover, by discoutinuin the distillation at the point mentioned, I fin that the residue is a viscous, oily mass, which I propose to employ as a lubricant.

It will be understood that the distillate which is taken ofi up to 250 0., may be subsequently refined by redistillatioii, and by that I mean with or without the presence of clay,'in accordance with the nature of the distillate and the product it is desired to finally obtain.

In the same manner, the distillate may be mitted to remain in the still and the distillation continued and the heavy fractions separately collected. In either case, of course, it

will be possible to collect various fractions and to'produce an oil which may meet a great variety of tests-for any particular use.

The effect of the clay ma be described as catalytic, since I do not fin that it is chemically changed or combines with the products to any appreciable degree, although in some cases, there may posibly be a chemical reaction between the material treated and the com nents of the clay. l

e clay may also exert various absorbent and adsorbent tendencies u n constituents of the material being treate as well as upon any moisture present, these being properties of the colloidal clays such as the bentonites.

Thedistillate obtained up to 250 0., I have found to possess a lower specific gravity than the turpentine originally charged and -der treatment, the clay employed,.the nature ,of the apparatus and the time and machine oil. In fact, I have found it in the particular case, here illustrated, a

specific gravity below substantially 0.858, namely 0.853, and, in man cases, the specific gravity will be considera ly lower, dependmg upon the amount of fractionating and the nature-of the material treated.

The amount of distillate obtained, of

course, will vary, but it will in most cases constitute substantially 50 to per cent of the original bulk of material being". treated.

The distillate is: found to possess chemical and physical characteristics different in varying degrees from the original material and this I attribute to the process of distillation described and, of course, will also vary with the nature of the clay employed.

The distillate forms a desirable solvent and one purpose for which it is especially useful is in the devulcanization and reclaiming of vulcanized rubber, as well as a solvent for various resins and gums Where the distillate contains heavier oil fractions it may, as stated, be used as a lubricant.

The oil which I have described above and referred to as a residue after the fract ons up'to 250 C., have been removed, will be useful as a lubricant and obviously for any other purposes to .which oils of the same char- .acter are applied.

..This oil is clear yellowish, has a bright flourescence,

agreeable odor and is quite viscous. The viscosity of the oil recovered has been found upon test, to be in the neighborhood of 130 Saybolt, with a flash point of about 240 F. (Cleveland open cup) and a content of residual carbon of substantially 0.05 per cent. In some cases, this oil need not -be redistilled or refined, but for lubricating purposes, as for instance, an automobile lubricant, itis desirable to raise the flash point and'viscosity, which I have done, by fractionating ofi possibly ten per cent of the lighter fractions, giving a flash point well over 300 F. and a proportionately increased viscosity.

The lubricating oil produced has Dleasing fluorescence, particularly. ng both'before and on redistillation ish tint,'which is comparable with 7 product or oils from other sources are used.

The specific gravity ofthe residual oil before it is'refined varies with the material untempera-- ture elements, but in the case of a turpentine treatment, it was substantially 0.9 to 1.00 more or less, so that it is comparable with form to a pro the petroleum oils obtained from most oil fields in this country, as well as abroad, It can be, as stated, subsequently refined to raise or-lower the flash point, burning point, viscosity and in than that obtained from mineral oils.

I have already stated that the fractionating may continue .to any desired extent, in accordance with the character of distillate it is-desired to obtain i. e. a solvent or lubricant, and have indicated as the usual point where the out between the solvent fractions and the lubricating fractions will be made as being about 250 C.

I have also stated that be again refined or distilled fractionally, if

general may be treated to connot equal if not more efficient the distillate may.

desired and that such distillation in either case may take place in the presence of the clay although this is not necessary.

I ave also stated that the oily. residue or the lubricating cut may be run off from the still and further refined by distillation or fractional distillation in the presence of the clay, as well as without the use of this agent, and also thatdistillation of the lubricating residue may continue in the still.

In referring to a specific treatment with one of the terpenes, namely turpentine from wood distillation or from gums, I do not mean to be limited to this specific product because, as stated, the invention is equally. useful in connection with a great variety of the terpenes, as well as vegetable, animal and essential oils and their homologues, many .of which contain terpene compounds and which will all be treated in substantially the same manner. It is possible naturally, that some modifications may be necessary by reason of the nature of the product being treated, as, for instance, its boiling range or where it is impure or is combined with other materials. but in general the process herein described will be followed.

In addition to bentonite or a clay or colloidal clay having the effect of bentonite the following may beused: Death Valley clay, wilkinite, montmorillionite, fullers earth, diatomaceous earth, infusorial earth, bauxite, kieselguhr, silica gel, pyrophillite, leverrierite, pipe clay. a

ave been particularly successful in the use of bentonite or colloidal clays relatedto bentonite or of the same series of which there are many members having various analyses but all generally similar and depending upon their source and occurrence.

Bentonite is the name given to a group or series of clayvlike materials having a content -of SiO about 58%,

and a content of about 22% of A1 0 with small contents of Fe O CaO, MgO, K 0 and others. Several of the clays above mentioned possess the same adsorbent andv absorbent tendencies of bentonite as well as a very similar analysis, while others may be treated in various ways to at uire similar characteristics. In referring to entonite n the claims, it is to be construed as covering true bentonites as well as clays of similar chemical analysis either raw or prepared, and

- tionating, and in fact entirely in either penod or in both periods. Naturally, the reaction will depend upon the materials treated, the agent employed, and the time and temperature elements.

The residual oil which I havereferred to as the lubricating cut will constitute anywhere from five to fifty per cent of the total bulk of material treated and, of course, is dependent upon the circumstances surrounding the operation. C

It is generally understood that the standard specific gravity for turpentine varies from 0.860 to 0.872 at 15.5 C. However, in some cases, a satisfactory turpentine 'may have as low a specific avity as.0.858, and a maximum of 0.875. giich products may be treated with equal efiiciency.

It will be observed that the distillate which I recover as the solvent cut, has a lower specific gravity than either of the turpentines employed and the lubricating cut possesses a specific gravity which in general is greater. In some cases, however, this lubricating cut will below .9 and as such, will be'a satisfactory lubricant without further treatment. '1

Furthermore, it will be understood that the quantity of clay may be increased or decreased with various results, depending upon the nature of the materials and other circumstances surrounding the operation and I have also discov'eredthat in many cases, the clay can be reused and that the operation can continue by adding a small quantity of fresh or green clay to that already in the still, without necessitating a fresh supply of clay for each operation,

In the treatment of the crude distillate from ordinary wood distillation whether by the destructive processor; the steam process,

thereoccurs a fraction which is, generally known asan intermediate fraction. The amount of thls fraction varies in each operation, but I have found that this intermediate fraction, which is a terpene, can be recovered and treated with equal facility by the process here described.

In the preliminary, heating to obtain the boiling of the bulk of'material, the time element cannot be definitely stated because I have found it to vary with different types of stills, as well as with difierent classes of materials and agents. In some cases, an hour will suflice for the preliminary heating, and an equal periodfor the maintaining of the constant temperature or boiling, but, 1n other cases, the periods may be longer and may vary.

As stated the material treated which is turpentine in the present case, by reason of the process described is caused to produce a fractional distillate of less specific gravity than the turpentine as well as a residual cut or oil residue of greater specific gravity. This is accomplished, of course, wlth the aid of the clay, but it will be noted that no recourse is had to pressure and that the temperatures employed are well within the range of cheap an eflicient operation, In some cases depending upon the circumstances or the nature of the clay and material as well as the apparatus available, some pressure may be required, but for many operations it is not crydene, tryclene, rosinoils, resin oils, pine oils, tar oils, rosin s irits, light oil, terpin, terpin hydrate, lina ool, caophyllene, humulene colophene and many others as well as oxidized'compounds, such as absinthol, borneol, cajeputol, carveol, carvone, camphors, cineol, citronellol, coriandrol, eucalyptol, fenchone, gerriiaiol and citral and many others may be use 1 Terpenes from the various wood oils, pine oils, oils produced from wood distlllatlon, oils from various pine oils, rosin oils,-tar 011s, oils from resinous wood, sawdust, oils from the treatment of tree and vegetable gums are those with which I have had the most success.

The essential oils, some of which include terpenes, in addition to 'those mentioned above are, benzine derivatives, resins i. e. oleo resins," thymol, menthol, oil of almonds, oil of bergamot, oil of cajeput, cedar oil, chamomile, cinnamon oil, oil of cloves, eucalyptus oil, geranium oil, lavender oil, oil of lemon, oil of peppermint, mustard oil, attar of roses, oil of sassafras, oil of Wintergreen, oil of rue and oil of Wormwood.

Some of the vegetable oils also. contain terpenes mentioned, I may treat cotton seed 011, 1m-

- seed oil, sesame, olive oil, soya bean 'oil, hem

oil, tung oil, sunflower oil, poppy oil, corn oi and castor oil, as well as palm oil and cocoanut oil.

Various animal oils including fish oils such as menhaden oil, liver oils, such as cod liver and in addition to those heretofore -mene, fenchene,"a-pinolene, b-pinolene, da-

, bl'ackfish oils, may likewise be treated.

It is obvious that various fractions may be collected separately and this applies both to the lighter fractions and the heavier ones.

Specificfractions have been and may be found useful for many purposes. I have stated that for light lubrlcating oils, for instance. it may be desirable to run above 250 (3., and in the same manner a lubricating cut or residue obtalned b runnmg at a lower range will provide a la ricating oil of greater viscosity useful for many applications.

Moreover, I have found thatafter distilling the lighter fractions and the heavier ones, a suitable pitch will be produced which is superior to the pitch obtained from usual sources. y

It will also be understood that the distillate to which I have referred is volatile and possesses a pleasing odor which is different from that of turpentine. C It will be understood that various of the lighter fractions may be collected and used separately. For instance, the fractions from 150 to 170 (3., will provide a satisfactory solvent, those from 17 0 to 190 C. an equally satisfactory solvent and those from 190 to 250 C., which are a very small part, a fraction which is not quite so satisfactory. I combine any one or more of these fractions to form a suitable solvent or I may useea'ch of them separately or combine all of them in a single distillate or volatile oil.

In addition to the fractions mentioned, I also use the fractions up to 150 with equal success, either combining them with the other fractions, or using the fractions individually.

What I claim is 1. The process of treating wood distillate fractions of the terpene serles derived from the direct distillation. of wood which comprises subjecting. at leastv one terpene wood distillate fraction to distillation in'the pres ence of a clay having the action of a catalyst, and collecting the resultant vapors.

2. The process of 'treating wood distillate fractions of the terpene serles derived from the direct distillation of wood which comprises treating at least oneterpene wood distillate fraction by distilling 03 a portion thereof in the presence of a clay havlng the action of .a catalyst, collecting resultant vapors, and recovering residual oil.

The process whichcomprises subjecting one of the oils ofthe terpene series" derived from the distillationof wood to gentle heating inthe presence of a clay having the action the'presence of the clay,

of a catalyst until the mass begins to boil, and

thereafter fractionally distilling the mass in .and collecting'the resultant vapors. p

4. The process which comprises subjecting one of the oils of the terpene series derived from the distillation of wood to a gentle heatturpentine by distilling off a and collecting fractions ing in the presence of a clay having a c atalytic action until the mass begins'to boil, and

thereafterdistilling off a portion of the 6. The process which comprises subjecting 5 turpentine to distillation in the presence of a clay of the bentonite type and collecting the vapors.

7. The process which comprises subjecting turpentine to distillation in the presence of a clay having a catalytic action and collecting at least one of the fractions obtained within a boiling range up to substantially 250 C. I

8. The process which comprises treating portion thereof in the presence of a clay having a catalytic action, collecting the fractions, and recovering as a residue an oil boiling above substantia'lly 250 C.

9. The process of treating turpentine to recover a distillate therefrom and a residual oil which comprises distilling the turpentine in the presenceof a clay of the bentonite 10'.'The process of treating turpentine to recover a distillate therefromvand a residual oil which comprises distilling the turpentine in the presence of a clay of the bentonite type, collecting the fractions within the boilmg range up to substantially 250 C. to obtain a distillate of lower specific gravity than the turpentine. and recovering as a'residue an. oil having a higher specific gravity than the turpentine.

'11. The process of treating turpentine to recover a distillate therefrom which oomprise'sdistilling the turpentine in the presence of a clay of the bentonitetype, collecting a "distillate having a specific gravity below that of the tu entine, and discontinuing distillathe bentonite type to a gentle heating below" the boiling point of the turpe tine.

distilling the turpentine in the presen of the clay,

sta'ntially 250 C.

13. The proce$ of treating turpentine which comprises subjecting the turpentine to boiling up to sub-- a gentle heating below its boiling temperature in the presence of a clay of the bentonite type, distilling a portion of mass in the presence of the clay, and recovering as a residue anoilha aboilmg' int above substantially p0 14. The Qrocess which comprises subjectinfg turpentme to distillation in the presence 0 a clay having a catalytic action, collecting the fractions boiling up to substantially 190 0., and recovering as a residue an 011 of higher specific vi than the turpentine. In testimony w ereo I have hereunto set my hand. A

TALIAFERBO JAMES FAIRLEY. 

